JP5319174B2 - Polycarbonate resin composition and molded body thereof - Google Patents

Description

  The present invention relates to a polycarbonate resin composition and a molded body thereof. More specifically, a polycarbonate resin composition useful as a housing for automobile parts, electronic devices, information devices, etc., which does not exhibit delamination after molding and has excellent impact resistance, bending strength, fluidity, chemical resistance, and the like. And a molded body thereof.

Many filler-filled polypropylenes are used as automobile parts, but have problems such as scratch-resistant whitening, texture transfer, and poor weld appearance. On the other hand, polycarbonate (PC) has the advantage of excellent mechanical properties such as impact strength, but has disadvantages such as poor fluidity and chemical resistance.
As an improved technique, PC / ABS alloy is proposed for fluidity, and PC / polyester (PBT, PET) alloy is proposed for chemical resistance. However, PC / ABS alloy is inferior in chemical resistance and weather resistance, and gloss (gloss) is too high, so that it cannot be used as an interior material as it is, and requires painting, resulting in increased costs, and thus its use is restricted. Further, PC / polyester (PBT, PET) has a problem that the effect of improving the fluidity is small, the hydrolysis resistance is poor, the gloss is high, and it is difficult to reduce the gloss. Both the PC / ABS alloy and the PC / polyester (PBT, PET) alloy have a drawback that the squeaking noise is high.
Therefore, an alloy of PC and polyolefin resin, especially an alloy of polypropylene (PP) and PC, is expected as a combination of materials to overcome these problems, but it is difficult to achieve compatibility, and therefore, surface impact is weak. Injection molding There were major problems such as delamination of the product, and practical application was difficult.

For example, Patent Document 1 proposes to use epoxy-modified SEBS as a compatibilizer for PP and PC, but PP and PC have no functional groups, and this method makes it difficult to improve tensile elongation and prevent delamination. It is.
Patent Document 2 proposes to use PC having a terminal aliphatic OH group and an epoxy group-containing PP as a compatibilizer for PP and PC at the time of melt-kneading, but the molecular weight of the epoxy group-containing PP is small. In addition, there is a limit to the effect of improving the elongation and impact strength, and the orientation is promoted during molding, and peeling occurs in severe bending.
Patent Document 3 proposes that PC having a terminal carboxyl group and PP containing an epoxy group be used as a compatibilizing agent for PP and PC at the time of melt-kneading, but the reaction effect is not sufficient, and elongation is increased. Improvement and delamination prevention effect are small.
Patent Document 4 proposes to use SEBS as a compatibilizer for PP and PC, but SEBS is also poorly compatible with PC, and this method makes it difficult to improve tensile elongation and prevent delamination. It is.
Patent Document 5 proposes to improve low-temperature impact properties by melt-kneading a copolymer of OH-terminated PC and ethylene-glycidyl methacrylate (GMA), but this method hardly improves flowability. I can't expect it. Moreover, no consideration is given to the combination with PP.
Patent Document 6 discloses a resin modifier obtained by reacting acid anhydride-modified polyolefin (PO) with OH-terminated PC, and that this modifier can also be used as a compatibilizer for PP and PC. Has proposed. However, the effect as a modifier for PC and PP is not shown in practice, and the reaction between acid anhydride-modified PO and OH is not sufficient, and the effect of improving elongation and preventing delamination is small.

JP-A-7-207078 Japanese Patent Laid-Open No. 63-215749 Japanese Patent Publication No. 8-19297 JP 2000-17120 A Japanese Patent Laid-Open No. 3-7758 JP-A-3-294333

  The present invention compensates for the disadvantages of aromatic polycarbonate resin inferior in fluidity and chemical resistance, is excellent in impact resistance, bending strength, fluidity and chemical resistance, etc. An object of the present invention is to provide a polycarbonate resin composition that can be made into a resin and a molded product thereof.

As a result of intensive studies to achieve the above object, the present inventors have found that (A) an aromatic polycarbonate resin having a predetermined molecular weight, (B) a specific polyolefin resin and / or polyolefin elastomer, (C) slurry weight Polypropylene resin by legal method, and (D) a polycarbonate resin obtained by blending at a specific ratio at least one selected from the group consisting of aliphatic amine salts, aromatic amine salts, ammonium hydroxides, and hydroxylammonium salts, and melt-kneading The inventors have found that the above object can be achieved by the composition, and have completed the present invention.
That is, this invention provides the following polycarbonate resin composition and its molded object.

1. (A) Aromatic polycarbonate resin having a viscosity average molecular weight of 16000 to 26000 50 to 94% by mass, (B) A polyolefin resin containing 3 to 30% by mass of an epoxy group or a glycidyl group and / or 1 to 15 mass of a polyolefin elastomer. % And (C) 100 parts by mass of a resin component comprising 5 to 40% by mass of a polypropylene resin produced by a slurry polymerization method, (D) aliphatic amine salt, aromatic amine salt, ammonium hydroxide, hydroxyl A polycarbonate resin composition comprising at least one 0.001-1 part by mass selected from the group of ammonium salts and melt kneaded.
2. (C) The polycarbonate resin composition according to 1 above, wherein the component has a melt index of 2 to 40 g / 10 min.
3. A molded article obtained by injection molding the polycarbonate resin composition according to 1 or 2 above.
4). The molded product according to 3 above, which is used for automobile parts.

  According to the present invention, it is possible to provide a polycarbonate resin composition that is excellent in fluidity and chemical resistance, excellent in impact resistance and bending strength even when an aromatic polycarbonate resin is blended, and molded by using this. It is possible to provide a molded article that does not exhibit layer peeling later and can be reduced in gloss.

  The polycarbonate resin composition of the present invention comprises (A) an aromatic polycarbonate resin having a predetermined molecular weight, (B) a specific polyolefin resin and / or polyolefin elastomer, (C) a polypropylene resin by slurry polymerization, and ( D) It contains at least one selected from the group consisting of aliphatic amine salts, aromatic amine salts, ammonium hydroxide, and hydroxylammonium salts.

[(A) Aromatic polycarbonate resin]
The (A) aromatic polycarbonate resin in the present invention is not particularly limited as long as it has a viscosity average molecular weight of 16000 to 26000. Usually, various aromatic polycarbonates produced by the reaction of a dihydric phenol and a carbonate precursor can be used.

Various divalent phenols may be mentioned, and in particular, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4- Hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) ether Bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide and bis (4-hydroxyphenyl) ketone. These dihydric phenols may be used alone or in combination of two or more.
Particularly preferred dihydric phenols are those based on bis (hydroxyphenyl) alkanes, especially bisphenol A or bisphenol A.

  Examples of the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate, specifically phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, and diethyl carbonate.

  The aromatic polycarbonate may have a branched structure, and examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4- Bidroxyphenyl) -1,3,5-triisopropylbenzene, phloroglysin, trimellitic acid, and isatin bis (o-cresol).

  The component (A) in the present invention has a viscosity average molecular weight of 16000 to 26000. When the viscosity average molecular weight is less than 16000, the tensile elongation and impact resistance are insufficient, and brittle fracture occurs in a high-speed falling weight test or the like. On the other hand, if it exceeds 26000, delamination of the molded product occurs and the tensile elongation decreases. The viscosity average molecular weight is preferably 17000 to 25000, and more preferably 18000 to 24000.

The viscosity average molecular weight of the component (A) in the present invention is a specific viscosity (η _sp ) measured by using an Ubbelohde viscometer with a solution obtained by dissolving about 0.7 g of an aromatic polycarbonate resin in 100 cm ³ of methylene chloride at 20 ° C. Is obtained by inserting into the following equation.
(Η _sp ) / C = [η] + 0.45 × [η] ² C
[η] = 1.23 × 10 ⁻⁵ M ^0.83
(However, [η] is the intrinsic viscosity and C is the polymer concentration.)

  The compounding quantity of (A) component in this invention is 50-94 mass% in the total amount of (A)-(C) component. If it is less than 50% by mass, the tensile strength, the elastic modulus and the like are lowered, and if it exceeds 94% by mass, improvement effects such as fluidity and chemical resistance become insufficient. Preferably it is 55-92 mass%, More preferably, it is 60-88 mass%.

[(B) Polyolefin resin or polyolefin elastomer]
The (B) polyolefin resin and / or polyolefin elastomer in the present invention contains 3 to 30% by mass of an epoxy group or a glycidyl group.

The polyolefin resin in the component (B) is, for example, an olefin homopolymer having an epoxy group or a glycidyl group, or a copolymer of an olefin and an unsaturated monomer having an epoxy group or a glycidyl group. The copolymer may be a copolymer of an unsaturated monomer having an epoxy group or a glycidyl group, and the copolymer is a graft copolymer, a random copolymer, or a block copolymer. Also good.
Further, for example, the terminal of the olefin polymer, or the unsaturated bond existing in the copolymer of olefin and other unsaturated monomer and the composite thereof, hydrogen peroxide, organic peracid, etc. An epoxy group may be introduced by oxidation with benzoic acid, performic acid, peracetic acid, or the like. That is, any olefin polymer may be used as long as an epoxy group or a glycidyl group is introduced.
The polyolefin-based elastomer in the component (B) is a low-crystalline or non-crystalline olefin-based copolymer containing an epoxy group or a glycidyl group and having a crystallinity measured by an X-ray diffraction method of 50% or less. is there.

Examples of olefins include ethylene, propylene, 1-butene, isobutylene, 2-butene, cyclobutene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 3-methyl-1-butene, 4- Examples include methyl-1-butene, cyclopentene, 1-hexene, cyclohexene, 1-octene, 1-decene, and 1-dodecene. These may be used alone or in combination of two or more.
Examples of the unsaturated monomer having an epoxy group or glycidyl group include glycidyl acrylate, glycidyl methacrylate, vinyl glycidyl ether, allyl glycidyl ether, methacryl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, glycidyl thinner. Mate, glycidyl itaconate, and N- {4- (2,3-epoxypropoxy) -3,5-dimethylbenzylmethacrylamide. These may be used alone or in combination of two or more.

  (B) Content of the epoxy group or glycidyl group in a component is 3-30 mass%. If it is less than 3% by mass, the effect of improving the compatibility between the component (A) and the component (C) is not exhibited, the tensile elongation and impact resistance are lowered, and delamination of the molded product occurs. On the other hand, if it exceeds 30% by mass, self-crosslinking may occur, the tensile elongation and impact resistance will be reduced, and delamination of the molded product will occur. Preferably it is 4-25 mass%, More preferably, it is 5-20 mass%.

  The weight average molecular weight of the component (B) is preferably about 50,000 to 500,000. Within this range, delamination can be prevented and good tensile elongation and high surface impact can be obtained. In addition, a weight average molecular weight can be calculated | required by using a gel permeation chromatography (GPC) method.

In the present invention, as the component (B), one or more polyolefin resins having an epoxy group or glycidyl group may be used, or one or more polyolefin elastomers having an epoxy group or glycidyl group may be used, Moreover, you may use together 1 or more types of the said polyolefin-type resin, and 1 or more types of polyolefin-type elastomer.
The compounding quantity of (B) component in this invention is 1-15 mass% in the total amount of (A)-(C) component. If it is less than 1% by mass, the compatibility between the component (A) and the component (C) cannot be improved sufficiently, the tensile elongation and the impact resistance are lowered, and further, the delamination of the molded product occurs. If it exceeds 15% by mass, self-crosslinking tends to occur, the tensile strength and elastic modulus are greatly reduced, and the fluidity is deteriorated. Preferably it is 2-13 mass%, More preferably, it is 3-10 mass%.

[(C) Polypropylene resin]
The (C) polypropylene resin in the present invention is produced by a slurry polymerization method.
As the component (C), propylene alone may be polymerized, or propylene may be mainly used as a copolymer. For example, it may be an isotactic propylene homopolymer or a syndiotactic propylene homopolymer. Examples of the copolymer include a copolymer of propylene and ethylene, and may be any of a graft copolymer, a random copolymer, and a block copolymer.

In the present invention, a slurry polymerization method is employed as the polymerization method for the component (C). When the component (C) polymerized by a gas phase polymerization method other than the slurry polymerization method is used, for example, the molecular weight of the PC is lowered, and the tensile elongation and impact resistance are lowered.
Regarding the conditions of the slurry polymerization method, a Ziegler catalyst is usually used as the catalyst, the polymerization temperature is about 30 to 90 ° C., the polymerization time is about 30 minutes to 10 hours, and the reaction pressure is about normal pressure 0.1 to 1 MPa. is there.
When a polymerization solvent is used, for example, aromatic hydrocarbons, alicyclic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons, and the like can be used. These solvents may be used alone or in combination of two or more.

  In the present invention, the component (C) preferably has a melt index (MI) of about 2 to 40 g / 10 minutes at a measurement condition of a resin temperature of 230 ° C. and a load of 21.18 N. When MI is 2 g / 10 min or more, the effect of improving the fluidity can be sufficiently exerted, and when it is 40 g / 10 min or less, delamination of the molded body hardly occurs. More preferably, it is 3-30 g / 10min. MI is determined by a measurement method based on ASTM D 1238.

In the present invention, as the component (C), one type of the propylene polymer may be used, or two or more types may be used in combination.
The compounding quantity of (C) component in this invention is 5-40 mass% in the total amount of (A)-(C) component. If the amount is less than 5% by mass, the effect of improving the fluidity and chemical resistance cannot be sufficiently exerted, and if it exceeds 40% by mass, the tensile elongation and impact resistance are lowered, and further, the layered product is easily peeled off. Preferably it is 7-35 mass%, More preferably, it is 10-30 mass%.

[(D) Aliphatic amine salt, aromatic amine salt, ammonium hydroxide, hydroxylammonium salt]
(D) component in this invention is at least 1 sort (s) chosen from the group of an aliphatic amine salt, an aromatic amine salt, ammonium hydroxide, and hydroxylammonium salt.
The aliphatic amine salt and the aromatic amine salt can be represented by, for example, the general formula R ¹ R ² R ³ N · 1 / nA ¹ , and in the case of the aliphatic amine salt, R ^{1 to} R ³ are independently hydrogen atoms. Or an aliphatic group (but not all hydrogen atoms at the same time). In the case of an aromatic amine salt, R ^{1 to} R ³ independently represent a hydrogen atom or an aromatic group (however, not all are hydrogen atoms at the same time). A ¹ represents an acid, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, chloric acid, perchloric acid, acetic acid, monoalkyl sulfuric acid, and sulfonic acid compounds. n is the valence of the anion acid A ^1, for example, in the case of hydrochloric acid n = 1, in the case of sulfuric acid it is n = 2.

Ammonium hydroxide can be represented, for example, by the general formula R ⁴ R ⁵ R ⁶ R ⁷ N ⁺ OH ⁻ . R ^{4 to} R ⁷ independently represent, for example, a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms (however, not all are hydrogen atoms at the same time).
Examples of this ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, and tetraisopropylammonium hydroxide.
On the other hand, the hydroxylammonium salt can be represented by, for example, the general formula R ⁸ R ⁹ NOH · 1 / mA ² , and R ⁸ and R ⁹ are, for example, independently a hydrogen atom or a straight chain having 1 to 5 carbon atoms, A branched alkyl group is shown (but not all hydrogen atoms at the same time). A ² represents an acid, and m is the valence of the anion of acid A ² .

Examples of the hydroxylammonium salts include methylhydroxylamine hydrochloride, ethylhydroxylamine hydrochloride, n-propylhydroxylamine hydrochloride, isopropylhydroxylamine hydrochloride, dimethylhydroxylamine hydrochloride, diethylamine hydrochloride, and hydrochloric acid in these hydroxylamines. And hydroxylamines substituted with sulfuric acid, nitric acid, acetic acid, monoalkyl sulfuric acid, sulfonic acid compounds and the like.
In the present invention, as the component (D), one type of the nitrogen-containing compound described above may be used, or two or more types may be used in combination.
The compounding quantity of (D) component in this invention is 0.001-1 mass part with respect to 100 mass parts of total amounts of (A)-(C) component. If it is less than 0.001 part by mass, delamination of the molded body tends to occur, and if it exceeds 1 part by mass, the tensile elongation and impact resistance may decrease. Preferably it is 0.002-0.8 mass part, More preferably, it is 0.003-0.5 mass part.

[Additive]
In the polycarbonate resin composition of the present invention, various additives can be blended in addition to the components (A) to (D) as long as the object of the present invention is not impaired. Examples of additives include inorganic additives, antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, flame retardant aids, colorants, antistatic agents, antiblocking agents, mold release agents, and lubricants. It is done.

[Polycarbonate resin composition and molded body]
The polycarbonate resin composition of the present invention can be obtained by blending the above components (A) to (D) and various additives by a conventional method, and melt-kneading. Examples of the melt kneader include a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, and a multi screw extruder. The heating temperature in melt kneading is usually 220 to 300 ° C.

The polycarbonate resin composition of the present invention is molded by applying a known molding method such as hollow molding, injection molding, extrusion molding, vacuum molding, pressure molding, hot bending molding, compression molding, calendar molding and rotational molding. A molding method by injection molding is particularly preferable.
In addition, the polycarbonate resin composition of the present invention is excellent in impact resistance, bending strength, fluidity and chemical resistance. Therefore, it is used as a housing for automobile parts, electronic devices and information devices that require these characteristics by injection molding. Is available.
That is, the present invention also provides a molded body using the polycarbonate resin composition of the present invention, particularly for automobile parts.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In the following, GMA represents glycidyl methacrylate, and MAH represents maleic anhydride. MI represents a melt index.

Components (A) to (D) used in Examples and Comparative Examples are shown below.
(A) Aromatic polycarbonate resin a-1: viscosity average molecular weight (Mv) 22000
a-2 (comparison): Viscosity average molecular weight (Mv) 15000
(B) Polyolefin resin or polyolefin elastomer b-1: Polypropylene-GMA graft copolymer [GMA content 8.1% by mass (3.68% by mass as glycidyl group)]
b-2: Ethylene-GMA copolymer [GMA content 12% by mass (5.46% by mass as glycidyl group)]
b-3 (Comparison): Polyethylene-GMA graft copolymer (GMA content 1.8% by mass)
b-4 (Comparison): Polypropylene-MAH graft copolymer (MAH content 5.3 mass%)
(C) Polypropylene resin c-1: Polypropylene block copolymer, MI: 10 g / 10 min, slurry polymerization method c-2: Polypropylene polymer, MI: 4 g / 10 min, slurry polymerization method c-3: Polypropylene block Copolymer, MI: 30 g / 10 min, gas phase polymerization method (D) At least one selected from the group consisting of aliphatic amine salts, aromatic amine salts, ammonium hydroxide, hydroxylammonium salts d-1: tetramethyl Ammonium hydroxide (Wako Pure Chemical Industries, Ltd., ammonium hydroxide)
d-2: Cation BB (trade name, manufactured by NOF Corporation, aliphatic amine salt type)

<Examples 1-5 and Comparative Examples 1-7>
After dry blending each component according to the blending ratio shown in Table 1 and Table 2, using a twin-screw kneader (TEX44, manufactured by Nippon Steel), a kneading block was used to increase the residence time at a set temperature of 250 ° C. Many were set, and melt kneading was performed while suppressing the discharge amount to obtain pellets.
After the obtained pellets were dried at 120 ° C. for 6 hours or longer, test pieces were prepared by injection molding (injection molding temperature: 270 ° C., mold temperature: 80 ° C.), and physical properties were evaluated by the following methods. The obtained results are shown in Tables 1 and 2.

<Evaluation of the physical properties>
(1) Tensile strength / tensile modulus / tensile elongation (test specimen thickness: 3.0 mm)
Conforms to JIS K 7162 (2) Izod impact strength (notched) (test piece thickness: 3.0 mm)
Conforms to JIS K 7110 (3) High-speed falling weight impact test (test plate 70 x 70 x 3 mm flat plate)
The measurement was performed with a ½ inch R hitting core and an impact speed of 7 m / sec.
The case where the fracture surface was ductile was evaluated as ○, and the case where the fracture surface was brittle was evaluated as ×.
(4) Surface Peeling The test piece was bent 180 degrees five times, and it was visually observed whether or not a peeling phenomenon occurred on the test piece (fine wrinkles were also peeled off).
The case where peeling was not observed was evaluated as ◯, and the case where peeling was observed even a little was evaluated as x.

<Examples 6 and 7>
Carbon black (manufactured by Mitsubishi Chemical Corporation) was added to the compositions of Examples 1 and 7 to give a black color, and pellets were obtained in the same manner as in Example 1. Using this pellet, a 140 × 140 × 2 mm embossed flat plate was formed by injection molding to prepare a test piece.
Using a Scratch Tester manufactured by Kato Tech, the surface of the test piece was subjected to a scratch test at a load of 30 N and a scratch speed of 100 mm / sec. Moreover, the hue was evaluated visually. The evaluation results are shown in Table 3.

<Comparative Examples 8 and 9>
Carbon black (manufactured by Mitsubishi Chemical Corporation) was further added to the compositions of Comparative Examples 2 and 4, respectively, and a test piece was prepared in the same manner as in Example 6 to conduct a scratch test, and the scratch whitening property was evaluated visually. . Moreover, the hue was evaluated visually. The evaluation results are shown in Table 3.

  Since the polycarbonate resin composition of the present invention is excellent in fluidity and chemical resistance, and is excellent in impact resistance and bending strength, it is useful for automobile parts, housings of electronic devices and information devices.

Claims (4)

  (A) Aromatic polycarbonate resin having a viscosity average molecular weight of 16000 to 26000 50 to 94% by mass, (B) A polyolefin resin containing 3 to 30% by mass of an epoxy group or a glycidyl group and / or 1 to 15 mass of a polyolefin elastomer. % And (C) 100 parts by mass of a resin component comprising 5 to 40% by mass of a polypropylene resin produced by a slurry polymerization method, (D) aliphatic amine salt, aromatic amine salt, ammonium hydroxide, hydroxyl A polycarbonate resin composition comprising at least one 0.001-1 part by mass selected from the group of lucammonium salts and melt-kneaded.   The polycarbonate resin composition according to claim 1, wherein the component (C) has a melt index of 2 to 40 g / 10 min.   The molded object formed by injection-molding the polycarbonate resin composition of Claim 1 or 2.   The molded article according to claim 3, which is used for automobile parts.